US10907003B2 - Method for preparing nitrile-based rubber - Google Patents

Method for preparing nitrile-based rubber Download PDF

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US10907003B2
US10907003B2 US16/315,049 US201716315049A US10907003B2 US 10907003 B2 US10907003 B2 US 10907003B2 US 201716315049 A US201716315049 A US 201716315049A US 10907003 B2 US10907003 B2 US 10907003B2
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nitrile
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based rubber
emulsifier
aliphatic hydrocarbon
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Jae Min Lee
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LG Chem Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • C08C1/14—Coagulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/22—Coagulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile

Definitions

  • the present invention relates to a method for preparing a nitrile-based rubber, and more particularly, to a method for preparing a nitrile-based rubber using an emulsifier comprising a C 30 to C 60 compound having two carboxyl groups.
  • a nitrile-based rubber is a polymer prepared by copolymerizing an ⁇ , ⁇ -unsaturated nitrile-based monomer such as acrylonitrile (ACN) and a conjugated diene-based monomer such as butadiene
  • the nitrile-based rubber has excellent oil resistance due to the use of an ⁇ , ⁇ -unsaturated nitrile-based monomer including a highly polar nitrile group, specifically, acrylonitrile, during preparation. Also, the content of the ⁇ , ⁇ -unsaturated nitrile-based monomer included in the nitrile-based rubber affects various vulcanization properties of the nitrile-based rubber.
  • acrylonitrile is used as the ⁇ , ⁇ -unsaturated nitrile-based monomer
  • resistance to hydrocarbon fuels and petroleum-based fluids is increased, and heat resistance, ozone resistance, wear resistance, tensile strength, hardness, and density are increased, but low temperature flexibility, rebound resilience, and gas permeability are decreased.
  • Nitrile-based rubbers are classified into 5 grades including a low nitrile (content of ACN in the rubber: 18 to 20%), a medium to low nitrile (content of ACN in the rubber: 28 to 29%), a medium nitrile (content of ACN in the rubber: 33 to 34%), a high nitrile (content of ACN in the rubber: 38 to 39%), and an ultra-high nitrile (content of ACN in the rubber: 45 to 48%), according to the content of the ⁇ , ⁇ -unsaturated nitrile-based monomer, for example, acrylonitrile (ACN).
  • ACN acrylonitrile
  • the high nitrile and the ultra-high nitrile are used in areas in which resistance to hydrocarbons having a high aromatic content, such as gasoline, is required.
  • the medium nitrile is used in a case where swelling of a rubber product is not an issue or oil has a low aromatic content.
  • the low nitrile and the medium to low nitrile are mainly used in the preparation of liquids having an insignificant swelling effect, such as paraffin oil or polyalphaolefin, or foamed heat insulating materials and hoses and the like, requiring low temperature characteristics such as low temperature resistance.
  • a C 12 -C 18 fatty acid including a monocarboxyl group or a rosin is mainly used.
  • the emulsifier during the emulsion polymerization, a relatively excessive amount of the emulsifier is introduced, and most of the emulsifier remains as an impurity in the nitrile-based rubber. For this reason, problems in that mechanical properties of a nitrile-based rubber prepared by emulsion polymerization deteriorate and the glass transition temperature range is broadened occur. Further, due to these problems, there are disadvantages in that the area to which the nitrile-based rubber is applied is limited and it is difficult to process the nitrile rubber.
  • An object of the present invention is to provide a method for preparing a nitrile-based rubber in which an amount of emulsifier used is decreased by using an emulsifier having a low critical micelle concentration and high thermal stability during polymerization.
  • An object of the present invention is to provide a method for preparing a nitrile-based rubber, by which it is possible to prepare a nitrile-based rubber having excellent mechanical properties by decreasing impurities in the nitrile-based rubber.
  • the present invention provides a method for preparing a nitrile-based rubber, by which the nitrile-based rubber is prepared by polymerizing a monomer mixture comprising an ⁇ , ⁇ -unsaturated nitrile-based monomer and a conjugated diene-based monomer, in the presence of an initiator; and an emulsifier comprising one or more compounds represented by the following Chemical Formula 1:
  • X 1 is a C 6 to C 20 tetravalent aromatic hydrocarbon or a C 2 to C 10 tetravalent aliphatic hydrocarbon,
  • R 1 to R 4 are the same as or different from each other, and each independently a C 2 to C 20 monovalent aliphatic hydrocarbon,
  • R 1 to R 4 are represented by —R 5 —COOH, and R 5 is a C 2 to C 20 divalent aliphatic hydrocarbon,
  • R 1 to R 5 comprise or do not comprise at least one unsaturated bond
  • a total sum of carbon atoms of X 1 and R 1 to R 4 is 30 to 60.
  • the present invention provides a nitrile-based rubber prepared by the method for preparing a nitrile-based rubber.
  • the present invention provides a nitrile-based rubber composition comprising the nitrile-based rubber.
  • emulsion polymerization can be smoothly carried out a smaller amount than the amount of a conventional emulsifier by using an emulsifier comprising a compound having 30 to 60 carbon atoms and having two carboxyl groups and having a low critical micelle concentration and excellent thermal stability.
  • mechanical properties of a nitrile-based rubber prepared by the method for preparing a nitrile-based rubber according to the present invention can be improved because the content of impurities derived from an emulsifier is decreased.
  • the critical micelle concentration may be measured by Brooklyn DV-III (spindle: 63).
  • a polymerization conversion ratio curve according to the ratio of an acrylonitrile-based monomer to butane over time under predetermined polymerization conditions may be drawn under each polymerization condition, and a polymerization conversion ratio according to the polymerization condition may be measured.
  • the nitrile-based rubber is prepared by polymerizing a monomer mixture comprising an ⁇ , ⁇ -unsaturated nitrile-based monomer and a conjugated diene-based monomer in the presence of an initiator and an emulsifier comprising one or more compounds represented by the following Chemical Formula 1.
  • the initiator may be a radical initiator, and the radical initiator may be one or more selected from the group consisting of an inorganic peroxide, an organic peroxide, and a nitrogen-based compound.
  • the inorganic peroxide may be one or more selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, potassium superphosphate, and hydrogen peroxide, and among them, ammonium persulfate is preferred.
  • the organic peroxide may be one or more selected from the group consisting of di-isobutyl hydroperoxide, t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanol peroxide, and t-butylperoxy isobutyrate, and among them, p-menthane hydroperoxide is preferred.
  • the nitrogen-based compound may be one or more selected from the group consisting of azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexane carbonitrile, and methyl azobisisobutyrate, and among them, azobis isobutyronitrile is preferred.
  • the organic peroxide is preferred.
  • the initiator may be introduced in an amount of 0.01 to 2 parts by weight, preferably, 0.03 to 1 part by weight, based on 100 parts by weight of the monomer mixture.
  • amount of initiator introduced satisfies the above-described range, a rubber having appropriate viscosity and excellent viscoelastic characteristics may be prepared. Further, preparation efficiency may be increased.
  • the emulsifier comprises one or more compounds represented by the following Chemical Formula 1.
  • X 1 is a C 6 to C 20 tetravalent aromatic hydrocarbon or a C 2 to C 10 tetravalent aliphatic hydrocarbon,
  • R 1 to R 4 are the same as or different from each other, and each independently a C 2 to C 20 monovalent aliphatic hydrocarbon,
  • R 1 to R 4 are represented by —R 5 —COOH, and R 5 is a C 2 to C 20 divalent aliphatic hydrocarbon,
  • R 1 to R 5 comprise or do not comprise at least one unsaturated bond
  • a total sum of carbon atoms of X 1 and R 1 to R 4 is 30 to 60.
  • the amount of emulsifier used may be significantly decreased because it is possible to implement a lower critical micelle concentration than that of a C 12 to C 18 fatty acid-based emulsifier in the related art. Accordingly, impurities derived from the emulsifier are decreased, so that the elastic modulus and thermal stability of a rubber product may be improved.
  • X 1 may be a C 6 to C 14 tetravalent aromatic hydrocarbon; a C 3 to C 10 tetravalent cyclic aliphatic hydrocarbon which comprises or does not comprise at least one unsaturated bond; or a C 2 to C 7 tetravalent linear or branched aliphatic hydrocarbon.
  • the C 6 to C 14 tetravalent aromatic hydrocarbon may be one or more selected from the group consisting of a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthracene ring.
  • C 3 to C 10 tetravalent cyclic aliphatic hydrocarbon may be represented by the following Chemical Formula 2 or 3.
  • C 2 to C 7 tetravalent linear or branched aliphatic hydrocarbon may be represented by the following Chemical Formula 4 or 5.
  • a 1 or A 2 may be the same as or different from each other, and each independently a direct bond, methylene, ethylene, propylene, or butylene, and
  • R 1 to R 4 may be the same as or different from each other, and each independently a C 2 to C 10 monovalent aliphatic hydrocarbon, two of R 1 to R 4 may be represented by —R 5 —COOH, and R 5 may be a C 2 to C 10 divalent aliphatic hydrocarbon.
  • the compound represented by Chemical Formula 1 has a length of the hydrophobic hydrocarbon chain in the molecule, which is 2 to 3-fold longer than that of a conventional C 12 to C 18 fatty acid emulsifier comprising a monocarboxyl group. Due to the long hydrophobic hydrocarbon chain, the compound represented by Chemical Formula 1 may have a low critical micelle concentration, a low content of unsaturated bonds, and excellent thermal stability compared to the conventional fatty acid emulsifier.
  • the compound represented by Chemical Formula 1 may be one or more selected from the group consisting of the following Chemical Formulae 1-1 to 1-12.
  • the compound represented by Chemical Formula 1 is one or more selected from the group consisting of the following Chemical Formulae 1-4, 1-6, and 1-11.
  • the emulsifier may comprise two or more different compounds among the compounds represented by Chemical Formula 1, and it is preferred that the emulsifier comprises all the compounds represented by Chemical Formulae 1-4, 1-6, and 1-11.
  • the compound represented by Chemical Formula 1-4 may be included in an amount of 45 to 70 wt %, preferably 50 to 65 wt %, and more preferably 55 to 60 wt %, based on the total weight of the compounds represented by Chemical Formulae 1-4, 1-6, and 1-11.
  • the compound represented by Chemical Formula 1-6 may be included in an amount of 15 to 40 wt %, preferably 20 to 35 wt %, and more preferably 25 to 30 wt %, based on the total weight of the compounds represented by Chemical Formulae 1-4, 1-6, and 1-11.
  • the compound represented by Chemical Formula 1-11 may be included in an amount of 1 to 25 wt %, preferably 5 to 20 wt %, and more preferably 10 to 15 wt %, based on the total weight of the compounds represented by Chemical Formulae 1-4, 1-6, and 1-11.
  • Two or more compounds represented by Chemical Formula 1 may be prepared during the preparation of the compound represented by Chemical Formula 1, and as a byproduct, one or more selected from the group consisting of a fatty acid having 45 to 60 carbon atoms and a fatty acid having 18 or less carbon atoms may be prepared. Accordingly, the emulsifier of the present invention may further comprise not only the compound represented by Chemical Formula 1, but also one or more selected from the group consisting of a fatty acid having 45 to 60 carbon atoms and a fatty acid having 18 or less carbon atoms.
  • the emulsifier comprising the compound represented by Chemical Formula 1 may have a critical micelle concentration of 20 to 40 mg/f at 25° C., and it is preferred that the emulsifier has a critical micelle concentration of 25 to 35 mg/i at 25° C.
  • the critical micelle concentration satisfies the above-described range, the degree of stability of the emulsion polymerization may be further increased due to the low critical micelle concentration.
  • the emulsifier comprising the compound represented by Chemical Formula 1 may have excellent stability against heat due to a fewer number of unsaturated bonds and a larger number of carbon atoms per molecule than those of a conventional emulsifier.
  • the emulsifier including the compound represented by Chemical Formula 1 may have a pH of 10 to 12 at 25° C., and it is preferred that the emulsifier has a pH of 10.5 to 11.5 at 25° C.
  • the emulsifier is stably dissolved in water, and may properly serve as an emulsifier, and since the emulsifier has appropriate emulsifying performance even in a lower temperature range than the conventional emulsifier, the activity of an initiator may be further improved.
  • the compound represented by Chemical Formula 1 may be directly synthesized, or those commercially available may be purchased and used.
  • the emulsifier may further comprise a metal salt of oleic acid.
  • metal salt of oleic acid an alkali metal salt of oleic acid is preferred, and a potassium salt of oleic acid is more preferred.
  • the emulsifier may comprise one or more compounds represented by Chemical Formula 1 and a metal salt of oleic acid at a weight ratio of 70:30 to 85:15, and it is preferred that the emulsifier comprises one or more compounds represented by Chemical Formula 1 and the metal salt of oleic acid at a weight ratio of 75:25 to 80:20.
  • the weight ratio satisfies the above-described range, even though a small amount of the emulsifier is introduced, emulsion polymerization may be easily performed, and for this reason, the content of impurities in the nitrile-based rubber is decreased, so that the thermal stability of the nitrile-based rubber, which is a final product, may become significantly excellent.
  • the emulsifier may be included in an amount of 0.3 to 3 parts by weight, more specifically, 0.5 to 1.5 parts by weight, based on 100 parts by weight of the monomer mixture.
  • the amount of impurities derived from the emulsifier in the nitrile-based rubber, which is a final product may be minimized while the polymerization reaction may be stably performed. Further, the impurities are minimized, so that mechanical properties of the nitrile-based rubber may be improved.
  • the ⁇ , ⁇ -unsaturated nitrile-based monomer may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ⁇ -chloronitrile, and ⁇ -cyanoethylacrylonitrile, and among them, acrylonitrile is preferred.
  • the conjugated diene-based monomer may be one or more selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, and isoprene, and among them, 1,3-butadiene is preferred.
  • the ⁇ , ⁇ -unsaturated nitrile-based monomer and the conjugated diene-based monomer may be introduced at a weight ratio of 15:85 to 45:55, preferably 18:72 to 40:60, and more preferably, 18:72 to 35:65.
  • a weight ratio satisfies the above-described range, a nitrile-based rubber having excellent flexibility, oil resistance, and tensile strength may be prepared.
  • the ⁇ , ⁇ -unsaturated nitrile-based monomer may be introduced collectively once or dividedly introduced two or more times.
  • a conjugated diene block may be suppressed from being generated in the nitrile-based rubber which is a final product.
  • the number of times of introducing the ⁇ , ⁇ -unsaturated nitrile-based monomer and the amount of ⁇ , ⁇ -unsaturated nitrile-based monomer introduced may be determined according to the polymerization conversion ratio.
  • the amount of ⁇ , ⁇ -unsaturated nitrile-based monomer introduced may be 50 to 60 wt % based on the total weight of the ⁇ , ⁇ -unsaturated nitrile-based monomer, when the polymerization conversion ratio is 20 to 25%, the amount of ⁇ , ⁇ -unsaturated nitrile-based monomer introduced may be 20 to 30 wt % based on the total weight of the ⁇ , ⁇ -unsaturated nitrile-based monomer and when the polymerization conversion ratio is 45 to 50%, the balance may be introduced.
  • the amount of ⁇ , ⁇ -unsaturated nitrile-based monomer introduced may be 50 to 60 wt % based on the total weight of the ⁇ , ⁇ -unsaturated nitrile-based monomer, when the polymerization conversion ratio is 15 to 20%, the amount of ⁇ , ⁇ -unsaturated nitrile-based monomer introduced may be 15 to 25 wt % based on the total weight of the ⁇ , ⁇ -unsaturated nitrile-based monomer, when the polymerization conversion ratio is 35 to 40%, the amount of ⁇ , ⁇ -unsaturated nitrile-based monomer introduced may be 10 to 15 wt % based on the total weight of the ⁇ , ⁇ -unsaturated nitrile-based monomer and when the polymerization conversion ratio is
  • the polymerization may be emulsion polymerization, and may be performed in a temperature range of 5 to 90° C., more specifically, 5 to 50° C.
  • an additive for facilitating the polymerization specifically, one or more selected from the group consisting of a molecular weight modifier, a chelating agent, an oxidizing-reducing agent, a dispersant, a pH adjuster, a deoxidizer, an anti-aging agent, and an oxygen scavenger may be further selectively used.
  • coagulation and drying may be further performed after the polymerization.
  • the coagulation may comprise treating the nitrile-based rubber latex with an aqueous inorganic salt solution and forming nitrile-based rubber latex coagulation.
  • the coagulation using salt may be a process for removing impurities (residual emulsifier, coagulant, and the like) from the nitrile-based rubber latex coagulation and obtaining a nitrile-based rubber.
  • the coagulation using salt may be performed by adding the nitrile-based rubber latex to an aqueous inorganic salt solution, and then drying the nitrile-based rubber coagulation.
  • the coagulation using salt is not particularly limited and may be performed by a typical method in the art, but specifically, the coagulation may be performed by heating the aqueous inorganic salt solution to 50 to 60° C., and then adding the nitrile-based rubber latex thereto, and stirring the resulting mixture for 10 minutes to 1 hour.
  • the aqueous inorganic salt solution is prepared by adding distilled water to an inorganic salt and mixing the resulting mixture, and the pH thereof is not particularly limited, but may be 10 to 12.
  • the inorganic salt may be one or more selected from the group consisting of potassium chloride, sodium chloride, manganese chloride, calcium chloride, magnesium sulfate, and aluminum sulfate.
  • the inorganic salt may be calcium chloride.
  • the drying is for removing remaining moisture in the nitrile-based rubber, and may be performed at 100 to 140° C., specifically, 100 to 120° C.
  • the drying satisfies the above-described conditions, the amount of remaining moisture in the nitrile-based rubber is appropriate, and thermal decomposition of the nitrile-based rubber does not occur.
  • a nitrile-based rubber prepared by the preparation method according to an exemplary embodiment of the present invention is provided.
  • the nitrile-based rubber according to another exemplary embodiment of the present invention may have a Mooney viscosity (ML 1+4 @ 100° C.) of 30 to 80.
  • a nitrile-based rubber composition comprising the nitrile-based rubber according to another exemplary embodiment of the present invention is provided.
  • the nitrile-based rubber composition comprises the nitrile-based rubber as a raw material rubber, and may further comprise an additive so as to satisfy functions and physical properties required according to the use of the nitrile-based rubber composition.
  • the additive may comprise one or more selected from the group consisting of a vulcanizing agent, a vulcanizing accelerator, a dispersant, a reinforcing filler, and a dissolution accelerator.
  • the vulcanizing agent may be one or more selected from the group consisting of powdered sulfur, sublimated sulfur, precipitated sulfur, surface-treated sulfur, insoluble sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, N,N′-dithio-bis(hexahydro-2H-azepinone), and polysulfide.
  • the vulcanizing accelerator may be one or more selected from the group consisting of zinc oxide, N-tert-butyl-2-benzothiazolesulfenamide (TBBS), and tetramethylthiuram monosulfite (TMTM).
  • the dispersant may be one or more selected from the group consisting of stearic acid, oleic acid, palmitic acid, and (anhydrous)maleic acid.
  • the reinforcing filler may be one or more selected from the group consisting of carbon black, silica, limestone, mica, clay, and bentonite.
  • the dissolution accelerator may be one or more selected from the group consisting of di(2-ethylhexyl)adipate, di(2-ethylhexyl)phthalate, and diisodecyl phthalate.
  • a molded article prepared by using a nitrile-based rubber composition comprising a nitrile-based rubber prepared by the method for preparing a nitrile-based rubber according to an exemplary embodiment of the present invention may exhibit excellent mechanical properties.
  • the nitrile-based rubber composition may have a tensile strength of 270 kg ⁇ f/cm 2 to 290 kg ⁇ f/cm 2 , an elongation of 470 to 500%, and a 300% modulus of 160 to 170 kg ⁇ f/cm 2 in accordance with ASTM D412.
  • a nitrile-based rubber latex coagulation was prepared by adding an aqueous calcium chloride solution thereto, such that the weight ratio of a prepared nitrile-based rubber latex and calcium chloride in the aqueous calcium chloride solution was 100:2, and heating the resulting mixture at 65° C. to perform coagulation.
  • a nitrile-based rubber was obtained by drying the nitrile-based rubber latex coagulation at 100° C. in an oven.
  • a nitrile-based rubber composition was prepared by introducing 1.5 parts by weight of sulfur as a vulcanizing agent, 3 parts by weight of zinc oxide and 0.7 part by weight of N-tert-butyl-2-benzothiazolesulfenamide (TBBS) as a vulcanizing accelerator, 1 part by weight of stearic acid as a dispersant, and 40 parts by weight of carbon black as a reinforcing filler based on 100 parts by weight of the obtained nitrile-based rubber into a reactor, and mixing the resulting mixture while stirring the mixture at 50 rpm at 50° C. for 8 minutes (pre-mixing for 1 minute and compounding for 7 minutes).
  • TBBS N-tert-butyl-2-benzothiazolesulfenamide
  • a nitrile-based rubber and a nitrile-based rubber composition were prepared in the same manner as in Example 1, except that 1.0 part by weight of a mixture, in which a fatty acid (CAS No. 67701-19-3) comprising a dimer acid and potassium oleate (CAS No. 143-18-0) were mixed at a weight ratio of 8:2, as an emulsifier was introduced thereinto, and the reaction time was 7.5 hours.
  • a fatty acid CAS No. 67701-19-3
  • a dimer acid and potassium oleate CAS No. 143-18-0
  • a nitrile-based rubber and a nitrile-based rubber composition were prepared in the same manner as in Example 1, except that 1.5 parts by weight of a mixture, in which a fatty acid (CAS No. 67701-19-3) comprising a dimer acid and potassium oleate (CAS No. 143-18-0) were mixed at a weight ratio of 8:2, as an emulsifier were introduced thereinto, and the reaction time was 7.5 hours.
  • a fatty acid CAS No. 67701-19-3
  • a dimer acid and potassium oleate CAS No. 143-18-0
  • a nitrile-based rubber and a nitrile-based rubber composition were prepared in the same manner as in Example 1, except that 2.0 parts by weight of a mixture, in which a fatty acid (CAS No. 67701-19-3) comprising a dimer acid and potassium oleate (CAS No. 143-18-0) were mixed at a weight ratio of 8:2, as an emulsifier were introduced thereinto, and the reaction time was 7.5 hours.
  • a fatty acid CAS No. 67701-19-3
  • a dimer acid and potassium oleate CAS No. 143-18-0
  • a nitrile-based rubber and a nitrile-based rubber composition were prepared in the same manner as in Example 1, except that 2.5 parts by weight of a mixture, in which a fatty acid (CAS No. 67701-19-3) comprising a dimer acid and potassium oleate (CAS No. 143-18-0) were mixed at a weight ratio of 8:2, as an emulsifier were introduced thereinto, and the reaction time was 7.4 hours.
  • a fatty acid CAS No. 67701-19-3
  • a dimer acid and potassium oleate CAS No. 143-18-0
  • Example 2 An experiment was performed in the same manner as in Example 1, except that 1.0 part by weight of a C 12 -C 18 fatty acid (CAS No. 67701-01-3) as an emulsifier was introduced thereinto, but the rubber was not formed.
  • a C 12 -C 18 fatty acid CAS No. 67701-01-3
  • a nitrile-based rubber and a nitrile-based rubber composition were prepared in the same manner as in Example 1, except that 2.0 parts by weight of a C 12 -C 18 fatty acid (CAS No. 67701-01-3) as an emulsifier were introduced thereinto, and the reaction time was 8.5 hours.
  • a C 12 -C 18 fatty acid CAS No. 67701-01-3
  • a nitrile-based rubber and a nitrile-based rubber composition were prepared in the same manner as in Example 1, except that 3.0 parts by weight of a C 12 -C 18 fatty acid (CAS No. 67701-01-3) as an emulsifier was introduced thereinto, and the reaction time was 7.8 hours.
  • a C 12 -C 18 fatty acid CAS No. 67701-01-3
  • Mooney viscosity The Mooney viscosity was measured by performing pre-heating with a large rotor at 100° C. for 1 minute and measuring and reading a value 4 minutes after the rotor was driven, using a Mooney viscometer (MV2000, Alpha Technologies Co., Ltd.).
  • C-Mooney viscosity After vulcanization at 145° C. for 45 minutes, the Mooney viscosity was measured by performing pre-heating with a large rotor at 100° C. for 1 minute and measuring and reading a value 4 minutes after the rotor was driven, using a Mooney viscometer (MV2000, Alpha Technologies Co., Ltd.).
  • Hardness After vulcanization at 145° C. for 45 minutes, the hardness was measured at 25° C. in accordance with ASTM D2240, and the unit is on the Shore D scale.
  • the maximum torque (MH) value during vulcanization at 170° C. was measured by using an oscillating disc rheometer.
  • Ts' time taken to achieve 1% vulcanization
  • Tc'90 time when the rubber composition is vulcanized to 90%
  • Tensile strength (kg ⁇ f/cm 2 ): After vulcanization at 145° C., the tensile strength of a 300% vulcanized product was measured in accordance with ASTM D412.
  • the nitrile-based rubber compositions in Examples 1 to 5 and the nitrile-based rubber compositions in Comparative Examples 2 and 3 were similar to each other in Mooney viscosity, hardness, and vulcanization characteristics.
  • the tensile strengths of the nitrile-based rubber compositions in Examples 1 to 5 were better by a maximum of 23.0 kg ⁇ f/cm 2 to a minimum of 9.9 kg ⁇ f/cm 2 , compared to those of the nitrile-based rubber compositions in Comparative Examples 2 and 3. Further, the elongations of the nitrile-based rubber compositions in Examples 1 to 5 were better by a maximum of 53% to a minimum of 14.9%, compared to those of the nitrile-based rubber compositions in Comparative Examples 2 and 3.
  • the 300% modulus of the nitrile-based rubber compositions in Examples 1 to 5 were better by a maximum of 15.9 kg ⁇ f/cm 2 to a minimum of 6.9 kg ⁇ f/cm 2 , compared to those of the nitrile-based rubber compositions in Comparative Examples 2 and 3.

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